The C9 position of cinchona alkaloids functions as a molecular hinge, with internal rotations around the C8C9 (τ1) and C9C4′ (τ2) bonds giving rise to four low energy conformers (1; anti‐closed, anti‐open, syn‐closed, and syn‐open). By substituting the C9 carbinol centre by a configurationally defined fluorine substituent, a fluorine‐ammonium ion gauche effect (σC−H→σC−F*; Fδ−⋅⋅⋅N+) encodes for two out of the four possible conformers (2). This constitutes a partial solution to the long‐standing problem of governing internal rotations in cinchonium‐based catalysts relying solely on a fluorine conformational effect. Fixed with fluorine! The C9 position of cinchona alkaloids functions as a molecular hinge, with internal rotations around the C8C9 (τ1) and C9C4′ (τ2) bonds giving rise to four low‐energy conformers. By substituting the C9 carbinol centre by a configurationally defined fluorine, a fluorine‐ammonium gauche effect encodes for two out of the four possible conformers. This constitutes a partial solution to the long‐standing problem of governing internal rotations in cinchonium‐based catalysts.